The present invention relates to thermographic recording materials whose prints have improved shelf-life image tone stability.
Thermal imaging or thermography is a recording process wherein images are generated by the use of thermal energy. In direct thermal thermography a visible image pattern is formed by image-wise heating of a recording material.
U.S. Pat. No. 3,218,166 discloses a heat-sensitive copy sheet product capable of providing high contrast dense black images on a white background when briefly heated at image areas to conversion temperature within the approximate range of 90-150xc2x0 C., said product containing, uniformly applied over a paperlike carrier and in position for heat-induced inter-reaction, reactants comprising a silver soap of an organic acid, a toner for the silver image, a di-tertiaryalkyl substituted phenol first reducing agent for the silver ion in an amount of at least about 0.01 mol per mol of silver soap and insufficient to form with said silver soap a dense image when briefly heated therewith, and a photosensitive different active-hydrogen aromatic organic second reducing agent for said silver ion in an amount no greater than that of said first reducing agent, said first reducing agent being further characterized as forming with an equal weight of silver behenate and one-fifth said weight of phthalazinone a uniformly blended trace deposit requiring at least six seconds preheat at 100xc2x0 C., before rapidly darkening at that temperature, and said second reducing agent on exposure to actinic radiation being rendered incapable of reducing silver ion on briefly heating with silver soap at 150xc2x0 C.
U.S. Pat. No. 3,547,648 discloses sheet material in copying processes, including a reactant layer comprising a silver soap of an organic acid, a tertiary-alkyl-substituted monophenol, and a tertiaryalkyl-substituted bisphenol, said substituted phenols each being a reducing agent for the silver ion and being characterized as forming with an equal weight of silver behenate and one fifth said weight of phthalazinone a uniformly blended trace deposit requiring at least six seconds preheat at 100xc2x0 C. before rapidly darkening at that temperature.
WO 97/34196 discloses a black and white thermographic element comprising a support bearing at least one, image-forming, thermographic emulsion layer comprising: (a) a non-photosensitive, reducible silver source; (b) a reducing agent system for silver ion; and (c) a binder; wherein said reducing agent system comprises: (i) at least one hindered phenol; and (ii) at least one co-developer of the formula 
wherein: R represents an aromatic group or an electron withdrawing group.
A thermographic element comprising a support bearing a support bearing at least one image-forming, thermographic emulsion layer comprising: (a) a non-photosensitive, reducible silver source; (b) a reducing agent system for said non-photosensitive, reducible silver source; and (c) a binder; wherein said reducing agent system comprises: (i) at least one hindered phenol; (ii) at least one co-developer of the formula R1xe2x80x94(Cxe2x95x90O)xe2x80x94NHNHxe2x80x94R2 wherein R1 represents hydrogen and R2 represents an aryl group; or, R1 represents hydrogen, alkyl or alkenyl of 1 to 20 carbon atoms; aryl, alkaryl, or aralkyl groups of up to 20 carbon atoms; aryloxy, thioaryloxy, or anilino groups of up to 20 carbon atoms; aliphatic or aromatic heterocyclic ring groups containing up to 6 ring atoms; carboxylic ring groups comprising up to 6 ring carbon atoms; or fused ring or bridging groups comprising up to 14 ring atoms; and R2 represents a trityl group; and (iii) at least one hydrogen atom donor compound of the formula: R3xe2x80x94H wherein R3xe2x80x94H represents an organic compound, the corresponding radical of which, R3xe2x80xa2, has a stability of from 350 to 6000 times that of a primary alkyl radical.
In printing with thermographic materials for medical applications for viewing with a light box, optimum diagnosis requires a blue-black image tone so that the higher ability of the human eye to distinguish detail with such image tone can be exploited, thereby improving the diagnostic value of such prints. Such image tone should be independent of the shelf-life of the thermographic recording material prior to printing and also of archival time after printing. Image tone can be assessed on the basis of the L*, a* and b* CIELAB-values as determined by spectrophotometric measurements according to ASTM Norm E179-90 in a R(45/0) geometry with evaluation according to ASTM Norm E308-90. Ingredients are required for substantially light-insensitive thermographic recording materials, which provide a balance of image tone stabilizing properties, enabling prints to be obtained with image tone which after pretempering is less dependent upon storage time prior to printing and to archival time after printing, while exhibiting image tone acceptable for radiologists viewing images in transmission on a light box.
It is therefore an aspect of the present invention to provide substantially light-insensitive black and white thermographic recording materials with improved image tone stability not only capable of producing prints with image tone which is less dependent upon storage time prior to printing.
Further objects and advantages of the invention will become apparent from the description hereinafter.
It has been surprisingly found that substantially light-insensitive thermographic recording materials comprising a thermosensitive element containing sterically hindered monophenols are capable of providing prints whose image tone is less dependent upon storage time prior to printing than prior art materials substantially light-insensitive thermographic recording materials.
Aspects of the present invention are provided by a substantially light-insensitive black and white thermographic recording material comprising a support and a thermosensitive element exclusive of bisphenol compounds, 4-substituted isoxazole compounds of the formula 
wherein R represents an aromatic group or an electron withdrawing group, organic compounds represented by R3xe2x80x94H, the corresponding radical of which, R3xe2x80xa2, has a stability of from 350 to 6000 times that of a primary alkyl radical, and photosensitive active-hydrogen aromatic organic reducing agents, the thermosensitive element containing at least one substantially light-insensitive organic silver salt, an organic reducing agent therefor in thermal working relationship therewith, an image tone stabilizer and a binder, characterized in that the image tone stabilizer is a sterically hindered monophenol.
Aspects of the present invention are also provided by a recording process comprising the steps of: (i) bringing an outermost layer of a thermographic recording material as described above into proximity with a heat source; (ii) applying heat from the heat source imagewise to the thermographic recording material in a substantially water-free condition while maintaining proximity to the heat source to produce an image; and (iii) removing the thermographic recording material from the heat source.
Use of a sterically hindered monophenol in a substantially light-insensitive thermographic recording material as an image tone stabilizer is also provided by the present invention.
Further advantages and embodiments of the present invention will become apparent from the following description.
According to a first aspect of the thermographic recording process, according to the present invention, the heat source is a thermal head.
According to a second aspect of the thermographic recording process, according to the present invention, the heat source is a thin film thermal head.
The term alkyl means all variants possible for each number of carbon atoms in the alkyl group i.e. for three carbon atoms: n-propyl and isopropyl; for four carbon atoms: n-butyl, isobutyl and tertiary-butyl; for five carbon atoms: n-pentyl, 1,1-dimethyl-propyl, 2,2-dimethylpropyl and 2-methyl-butyl etc.
By substantially light-insensitive is meant not intentionally light sensitive.
By the expression xe2x80x9cortho to the hydroxy groupxe2x80x9d is meant covalently bonded to the carbon atoms immediately adjacent to the carbon atom to which the hydroxy group is covalently bonded.
A fatty acid is an organic monobasic acid of general formula CnH2n+1COOH derived from the saturated series of aliphatic hydrocarbons, such as palmitic acid, stearic acid, behenic acid and arichidic acid.
Heating in a substantially water-free condition as used herein, means heating at a temperature of 80 to 250xc2x0 C. The term xe2x80x9csubstantially water-free conditionxe2x80x9d means that the reaction system is approximately in equilibrium with water in the air, and water for inducing or promoting the reaction is not particularly or positively supplied from the exterior to the element. Such a condition is described in T. H. James, xe2x80x9cThe Theory of the Photographic Processxe2x80x9d, Fourth Edition, Macmillan 1977, page 374.
According to the present invention a substantially light-insensitive black and white thermographic recording material is provided comprising a support and a thermosensitive element exclusive of bisphenol compounds, 4-substitute isoxazole compounds of the formula 
wherein R represents an aromatic group or an electron withdrawing group, organic compounds represented by R3xe2x80x94H, the corresponding radical of which, R3xe2x80xa2, has a stability of from 350 to 6000 times that of a primary alkyl radical, and photosensitive active-hydrogen aromatic organic reducing agents, the thermosensitive element containing at least one substantially light-insensitive organic silver salt, an organic reducing agent therefor in thermal working relationship therewith, an image tone stabilizer and a binder, characterized in that the image tone stabilizer is a sterically hindered monophenol.
According to a first aspect of the substantially light-insensitive thermographic recording material, according to the present invention, the sterically hindering groups in the sterically hindered monophenol are alkyl and cycloalkyl groups ortho to the hydroxy group.
According to a second aspect of the substantially light-insensitive thermographic recording material, according to the present invention, the sterically hindering groups in the sterically hindered monophenol ortho to the hydroxy group are selected from the group consisting of optionally substituted isopropyl, tertiary butyl, isobutyl, tertiary octyl, cyclopentyl and cyclohexyl groups.
According to a third aspect of the substantially light-insensitive thermographic recording material, according to the present invention, the sterically hindered monophenol has substituents other than the sterically hindering groups ortho to the hydroxy group selected from the group consisting of optionally substituted alkyl, cycloalkyl, alkoxy, aryloxy, carboxy and carboxyalkyl groups.
Suitable image tone stabilizing compounds according to the present invention are:
According to a fourth aspect of the substantially light-insensitive thermographic recording material, according to the present invention, the image tone stabilizer is 3,5-di-tert-butyl-4-hydroxybenzoic acid (ITS-1).
The thermosensitive element as used herein is that element which contains all the ingredients which contribute to image formation. According to the substantially light-insensitive thermographic recording material of the present invention the thermosensitive element is exclusive of bisphenol compounds, 4-substituted isoxazole compounds of the formula 
wherein R represents an aromatic group or an electron withdrawing group, organic compounds represented by R3xe2x80x94H, the corresponding radical of which, R3, has a stability of from 350 to 6000 times that of a primary alkyl radical, and photosensitive active-hydrogen aromatic organic reducing agents. The thermosensitive contains a substantially light-insensitive organic silver salt, an organic reducing agent therefor in thermal working relationship therewith, a sterically hindered phenol image tone stabilizer and a binder.
According to a fifth aspect of the substantially light-insensitive thermographic recording material, according to the present invention, the thermosensitive element is exclusive of 4-substituted isoxazole compounds.
According to a sixth aspect of the substantially light-insensitive thermographic recording material, according to the present invention, the thermosensitive element is exclusive of hydrogen atom donor compounds.
According to a seventh aspect of the substantially light-insensitive thermographic recording material, according to the present invention, the thermosensitive element is exclusive of hydrazide compounds.
According to a eighth aspect of the substantially light-insensitive thermographic recording material, according to the present invention, the thermosensitive element comprises a layer system in which the above-mentioned ingredients may be dispersed in different layers, with the proviso that the substantially light-insensitive organic silver salt is in reactive association with the reducing agent i.e. during the thermal development process the reducing agent must be present in such a way that it is able to diffuse to the particles of substantially light-insensitive organic silver salt so that reduction to silver can occur.
According to a ninth aspect of the substantially light-insensitive thermographic recording material, according to the present invention, the substantially light-insensitive organic silver salt is a substantially light-insensitive silver salt of an organic carboxylic acid.
According to a tenth aspect of the substantially light-insensitive thermographic recording material, according to the present invention, the substantially light-insensitive silver salt is a silver salt of an aliphatic carboxylic acid.
According to an eleventh aspect of the substantially light-insensitive thermographic recording material, according to the present invention, the substantially light-insensitive silver salt is a silver salt of a fatty acid.
According to a twelfth aspect of the substantially light-insensitive thermographic recording material, according to the present invention, the substantially light-insensitive silver salt is a silver salt of an aliphatic carboxylic acid, wherein the aliphatic carbon chain has between 12 and 30 C-atoms, e.g. silver laurate, silver palmitate, silver stearate, silver hydroxystearate, silver oleate and silver behenate, which silver salts are also called xe2x80x9csilver soapsxe2x80x9d.
According to an thirteenth aspect of the substantially light-insensitive thermographic recording material, according to the present invention, the substantially light-insensitive silver salt is an organic carboxylic acid as described in GB-P 1,439,478, e.g. silver benzoate.
Combinations of different silver salts of an organic carboxylic acids may also be used in the present invention, as disclosed in EP-A 964 300, hereby incorporated by reference.
Organic silver salts may be dispersed by standard dispersion techniques e.g. using ball mills, bead mills, microfluidizers, ultrasonic apparatuses, rotor stator mixers etc. have been found to be useful in this regard. Mixtures of organic silver salt dispersions produced by different techniques may also be used to obtain the desired thermographic properties e.g. of coarser and a more finely ground dispersions of organic silver salts.
According to a fourteenth aspect of the substantially light-insensitive thermographic recording material, according to the present invention, the organic reducing agent for the reduction of the substantially light-insensitive organic silver salt is an organic compound containing at least one active hydrogen atom linked to O, N or C, such as is the case with, aromatic di- and tri-hydroxy compounds.
According to a fifteenth aspect of the substantially light-insensitive-thermographic recording material, according to the present invention, the organic reducing agent is a 1,2-dihydroxybenzene derivative, such as catechol, 3-(3,4-dihydroxyphenyl) propionic acid, 1,2-dihydroxybenzoic acid, gallic acid and esters e.g. methyl gallate, ethyl gallate, propyl gallate, tannic acid, and 3,4-dihydroxy-benzoic acid ester.
According to an sixteenth aspect of the substantially light-insensitive thermographic recording material, according to the present invention, the organic reducing agent is an organic reducing agent disclosed in EP-B 692 733, herein incorporated by reference, e.g. ethyl 3,4-dihydroxybenzoate and n-butyl 3,4-dihydroxybenzoate.
According to a seventeenth aspect of the substantially light-insensitive thermographic recording material, according to the present invention, is an organic reducing agent disclosed in EP-A 903 625, herein incorporated by reference, e.g. 3,4-dihydroxybenzonitrile.
Combinations of reducing agents may also be used that on heating become reactive partners in the reduction of the substantially light-insensitive organic silver salt containing mixed crystals of two or more organic silver salts. For example, combinations of sterically hindered phenols with sulfonyl hydrazide reducing agents such as disclosed in U.S. Pat. No. 5,464,738; trityl hydrazides and formyl-phenyl-hydrazides such as disclosed in U.S. Pat. No. 5,496,695; trityl hydrazides and formyl-phenyl-hydrazides with diverse auxiliary reducing agents such as disclosed in U.S. Pat. No. 5,545,505, U.S. Pat. No. 5.545.507 and U.S. Pat. No. 5,558,983; acrylonitrile compounds as disclosed in U.S. Pat. No. 5,545,515 and U.S. Pat. No. 5,635,339; and 2-substituted malonodialdehyde compounds as disclosed in U.S. Pat. No. 5,654,130.
According to an eighteenth aspect of the substantially light-insensitive thermographic recording material, according to the present invention, the binder is a natural, modified natural or synthetic resins or mixtures of such resins, in which the substantially light-insensitive organic silver salt can be homogeneously dispersed either in aqueous or solvent media: e.g. cellulose derivatives such as ethylcellulose, cellulose esters, e.g. cellulose nitrate, carboxymethylcellulose, starch ethers, galactomannan, polymers derived from xcex1,xcex2-ethylenically unsaturated compounds such as polyvinyl chloride, after-chlorinated polyvinyl chloride, copolymers of vinyl chloride and vinylidene chloride, copolymers of vinyl chloride and vinyl acetate, polyvinyl acetate and partially hydrolyzed polyvinyl acetate, polyvinyl alcohol, polyvinyl acetals that are made from polyvinyl alcohol as starting material in which only a part of the repeating vinyl alcohol units may have reacted with an aldehyde, preferably polyvinyl butyral, copolymers of acrylonitrile and acrylamide, polyacrylic acid esters, polymethacrylic acid esters, polystyrene and polyethylene or mixtures thereof.
According to a nineteenth aspect of the substantially light-insensitive thermographic recording material, according to the present invention, the binder is a water-soluble film-forming binder, for example: polyvinyl alcohol, polyacrylamide, polymethacrylamide, polyacrylic acid, polymethacrylic acid, polyvinylpyrrolidone, polyethyleneglycol, proteinaceous binders such as gelatine, modified gelatines such as phthaloyl gelatine, polysaccharides, such as starch, gum arabic and dextran and water-soluble cellulose derivatives.
According to a twentieth aspect of the substantially light-insensitive thermographic recording material, according to the present invention, the binder is gelatin.
According to a twenty-first aspect of the substantially light-insensitive thermographic recording material, according to the present invention, the weight ratio of binder to substantially light-insensitive organic silver salt is in the range of 0.2 to 7.
According to a twenty-second aspect of the substantially light-insensitive thermographic recording material, according to the present invention, the thickness of the thermosensitive element is in the range of 5 to 50 xcexcm.
According to an twenty-third aspect of the substantially light-insensitive thermographic recording material, according to the present invention, the binder does not contain additives or impurities which adversely affect the thermographic properties of the substantially thermographic recording material.
According to a twenty-fourth aspect of the substantially light-insensitive thermographic recording material, according to the present invention, the thermosensitive element further contains a toning agent in order to obtain a neutral black image tone in the higher densities and neutral grey in the lower densities.
According to a twenty-fifth aspect of the substantially light-insensitive thermographic recording material, according to the present invention, the thermosensitive element further contains at least one toning agent selected from the group consisting of phthalimides and phthalazinones. Suitable toning agents are those within the scope of the general formulae described in U.S. Pat. No. 4,082,901. Further reference is made to the toning agents described in U.S. Pat. Nos. 3,074,809, 3,446,648 and 3,844,797.
According to a twenty-sixth aspect of the substantially light-insensitive thermographic recording material, according to the present invention, the thermosensitive element contains at least one heterocyclic toning compounds of the benzoxazine dione or naphthoxazine dione type as disclosed in GB 1,439,478, U.S. Pat. No. 3,951,660, e.g. benzo[e][1,3]oxazine-2,4-dione and 7-methyl-benzo[e][1,3]oxazine-2,4-dione, and U.S. Pat. No. 5,599,647, e.g. 7-(ethylcarbonato)-benzo[e][1,3]oxazine-2,4-dione, herein incorporated by reference.
According to a twenty-seventh aspect of the substantially light-insensitive thermographic recording material, according to the present invention, the substantially light-insensitive thermographic recording material further contains an antifoggant to obtain improved shelf-life and reduced fogging.
According to a twenty-eighth aspect of the substantially light-insensitive thermographic recording material, according to the present invention, the substantially light-insensitive thermographic recording material further contains at least one antifoggant selected from the group consisting of benzotriazole, substituted benzotriazoles, tetrazoles, mercaptotetrazoles such as 1-phenyl-5-mercapto-tetrazole, and aromatic polycarboxylic acids such as ortho-phthalic acid, 3-nitro-phthalic acid, tetrachlorophthalic acid, mellitic acid, pyromellitic acid and trimellitic acid, and anhydrides thereof.
According to a twenty-ninth aspect of the substantially light-insensitive thermographic recording material, according to the present invention, the thermosensitive element further comprises at least one polycarboxylic acid and/or anhydride thereof in a molar percentage of at least 15 with respect to all the organic silver salt(s) present and in thermal working relationship therewith.
According to a thirtieth aspect of the substantially light-insensitive thermographic recording material, according to the present invention, the thermosensitive element further comprises at least one aliphatic (saturated as well as unsaturated aliphatic and also cycloaliphatic) or aromatic polycarboxylic acid, optionally substituted and optionally used in anhydride form or partially esterified form on the condition that at least two free carboxylic acids remain or are available in the heat recording step.
Surfactants and dispersants aid the dispersion of ingredients or reactants which are insoluble in the particular dispersion medium.
According to a thirty-first aspect of the substantially light-insensitive thermographic recording material, according to the present invention, the substantially light-insensitive thermographic recording material further comprises one or more surfactants, which may be anionic, non-ionic or cationic surfactants, and/or one or more dispersants.
The recording material may contain in addition to the ingredients mentioned above other additives such as antistatic agents, e.g. non-ionic antistatic agents including a fluorocarbon group as e.g. in F3C(CF2)6CONH(CH2CH2O)xe2x80x94H, silicone oil, e.g. BAYSILON(trademark) MA (from BAYER AG, GERMANY).
The support for the thermosensitive element according to the present invention may be transparent, translucent or opaque and is a thin flexible carrier made of transparent resin film, e.g. made of a cellulose ester, cellulose triacetate, polypropylene, polycarbonate or polyester, e.g. polyethylene terephthalate.
The support may be in sheet, ribbon or web form and subbed if need be to improve the adherence to the thereon coated thermosensitive element. It may be pigmented with a blue pigment as so-called blue-base. One or more backing layers may be provided to control physical properties such as curl and static.
According to a thirty-second aspect of the substantially light-insensitive thermographic recording material, according to the present invention, the thermosensitive element is provided with a protective layer to avoid local deformation of the thermosensitive element and to improve resistance against abrasion.
According to a thirty-third aspect of the substantially light-insensitive thermographic recording material, according to the present invention, the thermosensitive element is provided with a protective layer comprising a binder, which may be solvent-soluble, solvent-dispersible, water-soluble or water-dispersible.
According to a thirty-fourth aspect of the substantially light-insensitive thermographic recording material, according to the present invention, the thermosensitive element is provided with a protective layer comprising a solvent-soluble polycarbonate binder as described in EP-A 614 769, herein incorporated by reference.
According to a thirty-fifth aspect of the substantially light-insensitive thermographic recording material, according to the present invention, the thermosensitive element is provided with a protective layer comprising a water-soluble or water-dispersible binders, as coating can be performed from an aqueous composition and mixing of the protective layer with the immediate underlayer can be avoided by using a solvent-soluble or solvent-dispersible binder in the immediate underlayer.
According to a thirty-sixth aspect of the substantially light-insensitive thermographic recording material, according to the present invention, the thermosensitive element is provided with a crosslinked protective layer.
According to a thirty-seventh aspect of the substantially light-insensitive thermographic recording material, according to the present invention, the thermosensitive element is provided with a protective layer crosslinked with crosslinking agents such as described in WO 95/12495, herein incorporated by reference.
According to a thirty-eighth aspect of the substantially light-insensitive thermographic recording material, according to the present invention, the thermosensitive element is provided with a protective layer comprising solid or liquid lubricants or combinations thereof for improving the slip characteristics of the substantially light-insensitive thermographic recording material.
According to a thirty-ninth aspect of the substantially light-insensitive thermographic recording material, according to the present invention, the thermosensitive element is provided with a protective layer comprising thermomeltable particles as solid lubricants are thermomeltable particles, such as those described in WO 94/11199, herein incorporated by reference.
According to a fortieth aspect of the substantially light-insensitive thermographic recording material, according to the present invention, the thermosensitive element is provided with a protective layer comprising a matting agent, such as described in WO 94/11198, herein incorporated by reference, e.g. talc particles, which optionally protrude from the protective layer.
The coating of any layer of the recording material of the present invention may proceed by any coating technique e.g. such as described in Modern Coating and Drying Technology, edited by Edward D. Cohen and Edgar B. Gutoff, (1992) VCH Publishers Inc. 220 East 23rd Street, Suite 909 New York, N.Y. 10010, U.S.A.
Thermographic imaging is carried out by the image-wise application of heat either in analogue fashion by direct exposure through an image or by reflection from an image, or in digital fashion pixel by pixel either by using an infra-red heat source, for example with a Nd-YAG laser or other infra-red laser, with a substantially light-insensitive thermographic material preferably containing an infra-red absorbing compound, or by direct thermal imaging with a thermal head.
In thermal printing image signals are converted into electric pulses and then through a driver circuit selectively transferred to a thermal printhead. The thermal printhead consists of microscopic heat resistor elements, which convert the electrical energy into heat via Joule effect. The operating temperature of common thermal printheads is in the range of 300 to 400xc2x0 C. and the heating time per picture element (pixel) may be less than 1.0 ms, the pressure contact of the thermal printhead with the recording material being e.g. 200-500 g/cm2 to ensure a good transfer of heat.
In order to avoid direct contact of the thermal printing heads with the outermost layer on the same side of the support as the thermosensitive element when this outermost layer is not a protective layer, the image-wise heating of the recording material with the thermal printing heads may proceed through a contacting but removable resin sheet or web wherefrom during the heating no transfer of recording material can take place.
Activation of the heating elements can be power-modulated or pulse-length modulated at constant power. EP-A 654 355 discloses a method for making an image by image-wise heating by means of a thermal head having energizable heating elements, wherein the activation of the heating elements is executed duty cycled pulsewise. EP-A 622 217 discloses a method for making an image using a direct thermal imaging element producing improvements in continuous tone reproduction.
Image-wise heating of the recording material can also be carried out using an electrically resistive ribbon incorporated into the material. Image- or pattern-wise heating of the recording material may also proceed by means of pixel-wise modulated ultra-sound.
Thermographic imaging can be used for the production of reflection type prints and transparencies, in particular for use in the medical diagnostic field in which black-imaged transparencies are widely used in inspection techniques operating with a light box.